Preparation of a novel TpBD (synthesized from phloroglucinol and benzidine) covalent organic framework (COF) immobilized open-tubular (OT) capillary is described by in situ growth strategy. The stationary phase in the column was characterized by Fourier transform infrared (FTIR) spectra, X-ray diffraction (XRD), thermogravimetric analysis (TGA), nitrogen adsorption–desorption isotherms, scanning electron microscope (SEM), transmission electron microscopy (TEM) and energy-dispersive X-ray spectrum (EDS). Several families of compounds with different properties (alkylbenzenes, parabens, sulfonamides and benzoic acids) were selected to evaluate the performance of the TpBD COF immobilized capillary. The results showed that the stationary phase was uniform with about 6.0 μm thickness under the optimal preparation conditions, and the relative standard deviations (RSDs) were no more than 3.13% of alkylbenzenes on the TpBD COF immobilized capillary for 11 consecutive runs, which exhibited its excellent reproducibility and stability. A rapid baseline separation of each family of the analytes (neutral parabens, amphoteric sulfonamides and acidic benzoic acids) was obtained in less than 6 min with a resolution (Rs) of 2.79~9.30, which sufficiently verified the rapid separation, high resolution and wide application range of the TpBD COF immobilized capillary, and further revealed this strategy of fabricating COF to capillary column to show great promise in capillary electrochromatography.